Package encapsulant compositions for use in electronic devices

ABSTRACT

A curable composition for encapsulating an electronic component comprises one or more mono- or polyfunctional maleimide compounds, or one or more mono- or polyfunctional vinyl compounds other than maleimide compounds, or a combination of maleimide and vinyl compounds, with a free radical curing agent, and optionally, one or more fillers.

The priority of U.S. provisional application No. 60/091,493 filing dateJul. 2, 1998 is claimed under 35 USC 119(e).

This application is a divisional of U.S. patent Ser. No. 09/336,246filing date Jun. 18, 1999 allowed.

FIELD OF THE INVENTION

This invention relates to package encapsulant compositions forelectronic devices that protect the electronic component and itsmetallization from environmental corrosion and mechanical damage.

BACKGROUND OF THE INVENTION

Microelectronic devices contain millions of electrical circuitcomponents, mainly transistors assembled in integrated circuit (IC)chips, but also resistors, capacitors, and other components. Theintegrated circuit component may comprise a single bare chip, a singleencapsulated chip, or an encapsulated package of single or multi-chips.These electronic components are interconnected to form the circuits, andeventually are connected to and supported on a carrier or substrate,such as a printed wire board.

The various materials used to manufacture the integrated circuits andtheir related interconnect materials are susceptible to environmental,moisture, and mechanical damage. Protection is provided by encapsulationof the electronic component within a polymeric material. Encapsulationcan be performed by a transfer molding process in which the component isloaded into a mold cavity, constrained, and the polymeric encapsulanttransferred from a reservoir into the cavity under pressure. Typically,the encapsulant is a thermosetting polymer, which then cross-links andcures to form the final assembly. Encapsulation also can be performed bydispensing an aliquot of polymeric encapsulant onto the component, suchas a chip or integrated circuit supported on a substrate, andsubsequently curing the composition.

For most commercial and industrial end uses, particularly thoseutilizing chip-on-board packages and multi-chip modules, theencapsulation is accomplished with polymeric thermosetting materials.The preferred thermosetting package encapsulation materials must have aviscosity and a thixotropic index that allows easy dispensability bysyringe, sufficient adhesion to the components, low ionic content toavoid corrosion of the metallization, adequate mechanical strength, highthermal and moisture resistance at application temperatures, and matchedcoefficient of thermal expansion to the materials it contacts.

For single chip packaging involving high volume commodity products, afailed chip can be discarded without significant loss. However, itbecomes expensive to discard multi-chip packages with only one failedchip, and the ability to rework the failed component would be amanufacturing advantage. Today, one of the primary thrusts within thesemiconductor industry is to develop not only a package encapsulant thatwill meet all the requirements for protection of the component, but alsoa package encapsulant that will be reworkable, allowing for the failedcomponent to be removed without destroying the substrate.

In order to achieve the required mechanical performance andreworkability, relatively high molecular weight thermoplastics would bethe preferred compositions for package materials. These materials,however, have high viscosity or even solid film form, which aredrawbacks to the manufacturing process. Therefore, there is a need fornew encapsulant compositions that are easily dispensable to conform withautomated manufacturing processes, and that are reworkable.

SUMMARY OF THE INVENTION

This invention is a curable encapsulant composition for electroniccomponents that comprises one or more compounds containing one or moremaleimide functionality, or one or more compounds containing one or morevinyl functionality, or a combination of compounds containing maleimideor vinyl functionality, a free-radical initiator and/or aphotoinitiator, and optionally one or more fillers.

A compound containing one maleimide functionality will be referred tohereinafter as a mono-functional maleimide compound. A compoundcontaining more than one maleimide functionality will be referred tohereinafter as a poly-functional maleimide compound. A compoundcontaining one vinyl functionality will be referred to hereinafter as amono-functional vinyl compound. A compound containing more than onevinyl functionality will be referred to hereinafter as a poly-functionalvinyl compound. The functionality is defined herein to be a carbon tocarbon double bond.

In another embodiment, this invention is also a cured encapsulantcomposition that results after the curing of the just described curableencapsulant composition.

In another embodiment, this invention is an electronic componentelectrically and mechanically connected to a substrate, encapsulated ina cured encapsulant composition, in which the cured encapsulant wasprepared from a composition comprising one or more mono- orpolyfunctional maleimide compounds, or one or more mono- orpolyfunctional vinyl compounds other than maleimide compounds, or acombination of maleimide and vinyl compounds, a free radical curingagent and/or a photoinitiator, and optionally one or more fillers.

DETAILED DESCRIPTION OF THE INVENTION

The maleimide and vinyl compounds used in the package encapsulantcompositions of this invention are curable compounds, meaning that theyare capable of polymerization, with or without crosslinking. As used inthis specification, to cure will mean to polymerize, with or withoutcrosslinking. Cross-linking, as is understood in the art, is theattachment of two polymer chains by bridges of an element, a moleculargroup, or a compound, and in general will take place upon heating. Ascross-linking density is increased, the properties of a material can bechanged from thermoplastic to thermosetting, which consequentlyincreases polymeric strength, heat-and electrical resistance, andresistance to solvents and other chemicals.

It is possible to prepare polymers of a wide range of cross-linkdensity, from tacky, elastomeric to tough glassy polymers, by thejudicious choice and amount of mono- or polyfunctional compounds. Thegreater proportion of polyfunctional compounds reacted, the greater thecross-link density.

If thermoplastic properties are desired, the package encapsulants ofthis invention can be prepared from mono-functional compounds to limitthe cross-link density. However, a minor amount of poly-functionalcompounds can be added to provide some cross-linking and strength to thecomposition, provided the amount of poly-functional compounds is limitedto an amount that does not diminish the desired thermoplasticproperties. Within these parameters, the strength and elasticity ofindividual package encapsulants can be tailored to a particular end-useapplication. The cross-link density can also be controlled to give awide range of glass transition temperatures in the cured encapsulant towithstand subsequent processing and operation temperatures.

In those cases where it is necessary to rework the assembly, athermoplastic composition should be chosen so that the electroniccomponent can be pried off the substrate. Any residue packageencapsulant can be heated until it softens and then be easily removed.

In the inventive package encapsulant compositions, the maleimidecompounds and the vinyl compounds may be used independently, or incombination. The maleimide or vinyl compounds, or both, will be presentin the curable package encapsulant compositions in an amount from 2 to98 weight percent based on the organic components present (excluding anyfillers).

The package encapsulant compositions will further comprise at least onefree-radical initiator, which is defined to be a chemical species thatdecomposes to a molecular fragment having one or more unpairedelectrons, highly reactive and usually short-lived, which is capable ofinitiating a chemical reaction by means of a chain mechanism. Thefree-radical initiator will be present in an amount of 0.1 to 10percent, preferably 0.1 to 3.0 percent, by weight of the maleimide orvinyl compound, or a combination of both maleimide and vinyl compounds(excluding any filler). The free radical curing mechanism gives a fastcure and provides the composition with a long shelf life before cure.Preferred free-radical initiators include peroxides, such as butylperoctoates and dicumyl peroxide, and azo compounds, such as2,2′-azobis(2-methyl-propanenitrile) and2,2′-azobis(2-methyl-butanenitrile).

Alternatively, the encapsulant compositions may contain aphotoinitiator, such as is sold by Ciba Specialty Chemicals under thetrademark Irgacure, in lieu of the free-radical initiator, and thecuring process may then be initiated by UV radiation. The photoinitiatorwill be present in an amount of 0.1 to 10 percent, preferably 0.1 to 3.0percent, by weight of the maleimide or vinyl compound, or a combinationof both maleimide and vinyl compounds (excluding any filler). In somecases, both photoinitiation and free-radical initiation may bedesirable. For example, the curing process can be started by UVirradiation, and in a later processing step, curing can be completed bythe application of heat to accomplish a free-radical cure.

In general, these compositions will cure within a temperature range of80° to 180° C., and curing will be effected within a length of time of 5minutes to 4 hours. As will be understood, the time and temperaturecuring profile for each encapsulant composition will vary, and differentcompositions can be designed to provide the curing profile that will besuited to the particular industrial manufacturing process.

Ease of application, even when thermoplastic properties are desired forthe package encapsulant, is achieved by using relatively low molecularweight reactive oligomers or pre-polymers and curing these in situ afterapplication to the electronic assembly of component and substrate.Applying the materials in an uncured state gives high processibility,and the resultant cured thermoplastic encapsulant provides highmechanical performance.

For some packaging operations, inert inorganic fillers are used in thepackage encapsulant to adjust the coefficient of thermal expansion tomore closely mirror that of the circuit interconnect, and tomechanically reinforce the interconnect. Examples of suitable thermallyconductive fillers include silica, graphite, aluminum nitride, siliconcarbide, boron nitride, diamond dust, and clays. The fillers will bepresent typically in an amount of 20-80 percent by weight of the totalpackage encapsulant composition.

As used throughout this specification: the notation C(O) refers to acarbonyl group.

Maleimide Compounds

The maleimide compounds suitable for use in the package encapsulantcompositions of this invention have a structure represented by theformula: [M—Ar _(m)]_(n)—Q, or by the formula: [M—Z _(m)]_(n)—Ar. Forthese specific formulae, when lower case “n” is the integer 1, thecompound will be a mono-functional compound; and when lower case “n” isan integer 2 to 6, the compound will be a poly-functional compound.

Formula [M—Ar _(m)]_(n)—Q represents those compounds in which: M is amaleimide moiety having the structure

in which

R¹ is H or C₁ to C₅ alkyl;

each Ar independently is an aromatic group selected from the aromaticgroups having the structures (I) through (V):

and Q is a linear or branched chain alkyl, alkyloxy, alkyl amine, alkylsulfide, alkylene, alkyleneoxy, alkylene amine, alkylene sulfide, aryl,aryloxy, or aryl sulfide species having up to about 100 atoms in thechain, which may contain saturated or unsaturated cyclic or heterocyclicsubstituents pendant from the chain or as part of the backbone in thechain, and in which any heteroatom present may or may not be directlyattached to Ar;

or Q is a urethane having the structure:

 in which each R² independently is an alkyl, aryl, or arylalkyl grouphaving 1 to 18 carbon atoms; R³ is an alkyl or alkyloxy chain having upto 100 atoms in the chain, which chain may contain aryl substituents; Xis O, S, N, or P; and n is 0 to 50;

or Q is an ester having the structure:

 in which R³ is an alkyl or alkyloxy chain having up to 100 atoms in thechain, which chain may contain aryl substituents;

or Q is a siloxane having the structure: —(CR¹ ₂)_(e)—[SiR⁴—O]_(f)—SiR⁴₂—(CR¹ ₂)_(g)— in which the R¹ substituent independently for eachposition is H or an alkyl group having 1 to 5 carbon atoms and the R⁴substituent independently for each position is an alkyl group having 1to 5 carbon atoms or an aryl group, and e and g are independently 1 to10 and f is 1 to 50; and

m is 0 or 1, and n is 1 to 6.

Preferably, Ar is structure (II), (III), (IV) or (V), and morepreferably is structure (II).

Preferably, Q is a linear or branched chain alkyl, alkyloxy, alkylene,or alkyleneoxy species having up to about 100 atoms in the chain, asdescribed with pendant saturated or unsaturated cyclic or heterocyclicsubstituents, or a siloxane as described, and more preferably is alinear or branched chain alkyl species or siloxane, as described.

Formula [M—Z _(m)]_(n)—Ar represents those compounds in which M is amaleimide moiety having the structure

in which

R¹ is H or C₁ to C₅ alkyl;

Z is a linear or branched chain alkyl, alkyloxy, alkyl amine, alkylsulfide, alkylene, alkyleneoxy, alkylene amine, alkylene sulfide, aryl,aryloxy, or aryl sulfide species having up to about 100 atoms in thechain, which may contain saturated or unsaturated cyclic or heterocyclicsubstituents pendant from the chain or as part of the backbone in thechain, and in which any heteroatom present may or may not be directlyattached to K;

or Z is a urethane having the structure:

 in which each R² independently is an alkyl, aryl, or arylalkyl grouphaving 1 to 18 carbon atoms; R³ is an alkyl or alkyloxy chain having upto 100 atoms in the chain, which chain may contain aryl substituents; Xis O, S, N, or P; and n is 0 to 50;

or Z is an ester having the structure:

 in which R³ is an alkyl or alkyloxy chain having up to 100 atoms in thechain, which chain may contain aryl substituents;

or Z is a siloxane having the structure: —(CR¹ ₂)_(e)—[SiR⁴₂—O]_(f)—SiR⁴ ₂—(CR¹ ₂)_(g)— in which the R¹ substituent independentlyfor each position is H or an alkyl group having 1 to 5 carbon atoms andthe R⁴ substituent independently for each position is an alkyl grouphaving 1 to 5 carbon atoms or an aryl group, and e and g areindependently 1 to 10 and f is 1 to 50;

Ar is an aromatic group selected from the aromatic groups having thestructures (VI) through (XIII) (although only one bond may be shown torepresent connection to the aromatic group K, this will be deemed torepresent any number of additional bonds as described and defined by n):

in which p is 1 to 100;

in which p is 1 to 100;

in which

R⁵, R⁶, and R⁷ are a linear or branched chain alkyl, alkyloxy, alkylamine, alkyl sulfide, alkylene, alkyleneoxy, alkylene amine, alkylenesulfide, aryl, aryloxy, or aryl sulfide species having up to about 100atoms in the chain, which may contain saturated or unsaturated cyclic orheterocyclic substituents pendant from the chain or as part of thebackbone in the chain, and in which any heteroatom present may or maynot be directly attached to the aromatic ring; or R⁵, R⁶, and R⁷ are asiloxane having the structure —(CR¹ ₂)_(e)—[SiR⁴ ₂—O]_(f)—SiR⁴₂—(CH₃)_(g)— in which the R¹ substituent is H or an alkyl group having 1to 5 carbon atoms and the R⁴ substituent independently for each positionis an alkyl group having 1 to 5 carbon atoms or an aryl group, and e is1 to 10 and f is 0 to 50;

and m is 0 or 1, and n is 1 to 6.

Preferably, Z is a linear or branched chain alkyl, alkyloxy, alkylene,or alkyleneoxy species having up to about 100 atoms in the chain, asdescribed with pendant saturated or unsaturated cyclic or heterocyclicsubstituents, or a siloxane as described, and more preferably is alinear or branched chain alkyl species or siloxane, as described.

Preferably, Ar is structure (VIII), (X) or (XI), more preferably isstructure (X) or (XI), and most preferably is structure (X).

The more preferred maleimide compounds, particularly for use asreworkable encapsulants, are N-butylphenyl maleimide and N-ethylphenylmaleimide.

Vinyl Compounds

The vinyl compounds (other than the maleimides) herein will have thestructure:

For these specific structures, when lower case “n” is the integer 1, thecompound will be a mono-functional compound; and when lower case “n” isan integer 2 to 6, the compound will be a poly-functional compound.

In these structures, R¹ and R² are H or an alkyl having 1 to 5 carbonatoms, or together form a 5 to 9 membered ring with the carbons formingthe vinyl group; B is C, S, N, O, C(O), O—C(O), C(O)—O, C(O)NH orC(O)N(R⁸), in which R⁸ is C₁ to C₅ alkyl; m is 0 or 1; n is 1-6; and Ar,Q, and Z are as described above.

Preferably, B is O, C(O), O—C(O), C(O)—O, C(O)NH or C(O)N(R⁸); morepreferably B is O, C(O), O—C(O), C(O)—O, or C(O)N(R⁸).

Other Composition Components

Depending on the nature of the substrate to which the packageencapsulant is to be bonded, the encapsulant may also contain a couplingagent. A coupling agent as used herein is a chemical species containinga polymerizable functional group for reaction with the maleimide andother vinyl compound, and a functional group capable of condensing withmetal hydroxides present on the surface of the substrate. Such couplingagents and the preferred amounts for use in compositions for particularsubstrates are known in the art. Suitable coupling agents are silanes,silicate esters, metal acrylates or methacrylates, titanates, andcompounds containing a chelating ligand, such as phosphine, mercaptan,and acetoacetate. When present, coupling agents typically will be inamounts up to 10 percent by weight, and preferably in amounts of 0.1-3.0percent by weight, of the maleimide and other monofunctional vinylcompound.

In addition, the encapsulant compositions may contain compounds thatlend additional flexibility and toughness to the resultant curedencapsulant. Such compounds may be any thermoset or thermoplasticmaterial having a Tg of 50° C. or less, and typically will be apolymeric material characterized by free rotation about the chemicalbonds, such as can be obtained by the presence of carbon-carbon doublebonds adjacent to carbon-carbon single bonds, the presence of ester andether groups, and the absence of ring structures. Suitable suchmodifiers include polyacrylates, poly(butadiene), polyTHF ( polymerizedtetrahydrofuran), CTBN (carboxy-terminated butyronitrile) rubber, andpolypropylene glycol. When present, toughening compounds may be in anamount up to about 15 percent by weight of the maleimide and othermonofunctional vinyl compound.

If siloxane moieties are not part of the maleimide or vinyl compoundstructure, siloxanes can be added to the package encapsulantformulations to impart elastomeric properties. Suitable siloxanes arethe methacryloxypropyl-terminated polydimethyl siloxanes, and theaminopropyl-terminated polydimethylsiloxanes, available from UnitedChemical Technologies.

Other additives, such as adhesion promoters, may also be added asneeded. The kinds and amounts of adhesion promoters that may be used areknown to those skilled in the art.

Another embodiment of this invention includes the maleimides having theformulae [M—Ar _(m)]_(n)—Q and [M—Z _(m)]_(n)—Ar as described herein inwhich Q and Z can be an ester having the structure

or the structure

in which

p is 1 to 100,

each R³ can independently be an alkyl or alkyloxy chain having up to 100atoms in the chain, which chain may contain aryl substituents, or

a siloxane having the structure —(CR¹ ₂)_(e)—[SiR⁴ ₂—O]_(f)—SiR⁴ ₂—(CR¹₂)_(g)— in which the R¹ substituent independently for each position is Hor an alkyl group having 1 to 5 carbon atoms, the R⁴ substituentindependently for each position is an alkyl group having 1 to 5 carbonatoms or an aryl group, e and g are independently 1 to 10 and f is 1 to50.

Another embodiment of this invention includes the vinyl compounds havingthe structures

as described herein in which B is C, S, N, O, C(O), C(O)NH or C(O)N(R⁸),in which R⁸ is C₁ to C₅ alkyl.

Another embodiment of this invention includes the vinyl compounds havingthe structures

as described herein in which Q and Z can be an ester having thestructure

or the structure

in which

p is 1 to 100,

each R³ can independently be an alkyl or alkyloxy chain having up to 100atoms in the chain, which chain may contain aryl substituents,

or a siloxane having the structure —(CR¹ ₂)_(e)—[SiR⁴ ₂—O]_(f)—SiR⁴₂—(CR¹ ₂)_(g)— in which the R¹ substituent independently for eachposition is H or an alkyl group having 1 to 5 carbon atoms, the R⁴substituent independently for each position is an alkyl group having 1to 5 carbon atoms or an aryl group, e and g are independently 1 to 10,and f is 1 to 50.

Another embodiment of this invention includes the composition asdescribed herein containing an anionic or cationic curing initiator. Thetypes and useful amounts of such initiators are well known in the art.

EXAMPLES

Various maleimide and vinyl compounds were prepared and formulated intopackage encapsulant compositions. The compositions were investigated forviscosity and thixotropic index for the uncured composition, and forcuring profile, glass transition temperature, coefficient of thermalexpansion, thermal mechanical analysis, and reworkability for the curedcomposition.

Example 1 Preparation of Benzamido-endcapped Dimer Diamine Bismaleimide

Dimer diamine (sold as Versamine 552 by Henkel, 20.0 g, 37 mmol) wassolvated in Et₂O (200 mL) in a 500 mL three-necked flask equipped withan addition funnel, magnetic stirring, internal temperature probe andnitrogen inlet/outlet. NaOH_(aq) (11. 7 mL of 6.25 M solution dilutedwith 100 mL H₂O, 73 mmol) was added with vigorous stirring. Thissolution was placed under a steady flow of nitrogen and cooled to 3° C.on an ice bath with stirring. The addition funnel was charged withp-nitrobenzoyl chloride (13.6 g, 73 mmol) in iethyl ether (Et₂O) (50mL), and this solution was added to the reaction vessel over the courseof 60 minutes, maintaining an internal T<10° C. The reaction was stirredat ˜3° C. for an additional 60 minutes after this addition was complete,then allowed to warm to room temperature and stirred for another 4hours. The solution was transferred to a separatory funnel and theisolated organic layer washed with distilled H₂O (300 mL), 5% HCl_(aq)(300 mL), NaCl_(aq) (250 mL) and distilled H₂O (2×250 mL). The organicswere isolated, dried over MgSO₄ anhyd., filtered and the solvent removedin vacuo to yield the dinitro compound as a viscous yellow oil whichexhibited acceptable ¹H NMR and IR spectra (30.0 g, 96%).

The dinitro compound described above (5.0 g, 5.9 mmol) was dissolved inmethanol (MeOH) (25 mL) and THF (5 mL) in a 250 mL three-necked flaskequipped with magnetic stirring, reflux condensor and nitrogeninlet/outlet. The solution was placed under nitrogen, and 5% Pd-C (0.96g) were added with stirring. Ammonium formate (3.4 g, 55 mmol) was addedand the reaction stirred at room temperature for 2 hours. Carbon dioxideevolution was immediately observed. The reaction solution was filtered,and bulk filtrate solvent was removed via rotary evaporator. Theresulting viscous oil was dissolved in diethyl ether (Et₂O) (150 mL),washed with distilled H₂O (150 mL), isolated and dried over MgSO₄ anhyd.Solvent was removed in vacuo to yield the diamine as a sticky tan oil,which exhibited acceptable ¹H NMR and IR spectra (3.9 g, 84%).

Maleic anhydride (0.5 g, 5.1 mmol) was dissolved in acetone (10 mL) in a250 mL three-necked flask equipped with magnetic stirring, additionfunnel and nitrogen inlet/outlet. The solution was cooled on an ice bathand placed under nitrogen. The addition funnel was charged with anacetone (10 mL) solution of the diamine described above (2.0 g, 2.60mmol), which was added dropwise over 30 minutes. The reaction wasstirred for an additional 30 minutes on the ice bath, then allowed towarm to room temperature, and stirred for another 4 hours. To theresulting slurry was added acetic anhydride (Ac₂O) (1.54 mL, 160 mmol),triethyl amine (Et₃N) (0.23 mL, 1.63 mmol) and sodium acetate (NaOAc)(0.16 g, 1.9 mmol). The resulting slurry was heated to mild reflux for 5hours. The reaction was allowed to cool to room temperature, and solventremoved via rotary evaporator to yield a brown oil. This material wasdissolved in CH₂Cl₂ (250 mL) and washed with distilled H₂O (200 mL),satd. NaHCO₃ (200 mL) and distilled H₂O (200 mL). Emulsions were brokenby adding NaCl when necessary. The organic layer was isolated, driedover MgSO₄ anhyd. and solvent removed in vacuo to yield thebismaleimide, a brown solid (2.0 g, 83%). The resin exhibitedsatisfactory ¹H NMR, ¹³C NMR and IR spectra, which indicated slightcontamination with acetic acid.

Example 2 Preparation of 20-Bismaleimido-10,11-dioctyl-eicosame (andisomers)

In a 5 L multi-neck flask equipped with a drying tube, thermometer, slowaddition funnel, mechanical stirrer and nitrogen purge maleic anhydride(98.06 g, 1.02 equivalents on —NH₂) was dissolved in 500 mltetrahydrofuran (THF). Stirring was begun and the solution was chilledwith a dry ice/water bath. Slow addition of dimer diamine (Versamine552, Henkel, 245.03 g, 0.4477 mol) in 250 ml THF was begun. Addition wascarried out over 1 hour. After addition was complete the ice bath wasremoved and 375 ml of THF was rinsed through the slow addition funnel toincorporate solidified diamine. After one hour the ice bath was replacedaround the flask. 1-Hydroxybenzotriazole (96.79 g, 0.80 equivalents on—NH₂) was added rinsing into the flask with 50 ml THF. When thetemperature had reached 5° C. slow addition of dicyclohexylcarbodiimide(DCC) (188.43 g, 1.02 equivalents on —NH₂) in 200 ml THF was begun. Thetemperature during addition was kept below ten degrees. After DCCaddition was complete the slow addition funnel was rinsed with 80 ml ofTHF. The ice bath was removed. The reaction was monitored by IR. When itappeared that the isoimide has been converted to maleimide(approximately 4 hours after the completion of DCC addition) the mixturewas filtered, rinsing the solids with THF. The orange solution wasplaced in the freezer overnight.

The solution was removed from the freezer and allowed to warm to roomtemperature. Hydroquinone (0.0513 g) was added to the solution. Apartial strip of the THF was carried out on a rotary evaporator with thetemperature maintained below 28° C. The solution was concentrated toapproximately 800 ml. Much particulate matter was visible. The solutionwas placed in freezer overnight.

The mixture was removed from the freezer and allowed to warm. The solidswere filtered, rinsing with THF. The filtrate was transferred to a 2 Lmulti-neck flask equipped with a mechanical stirrer, vacuum lineconnected to a trap, and a glass tube attached by tubing to a dryingtube. The remaining THF was stripped at room temperature by pulling avacuum and bubbling air through the material while stirring. Theresultant thick, creamy-tan colored semi-solid was placed in the freezerovernight.

The semi-solid was removed from the freezer and allowed to warm. Thesemi-solid was dissolved in 450 ml each of methanol and hexane, andwashed with 50% methanol/water (4×250 ml) to remove1-hydroxybenzotriazole (HOBT). It was attempted to extract the productwith hexane. After addition of 300 ml of hexane separation was notobserved. The mixture was washed with additional water (3×250 ml). Theorganic phase was placed in the freezer overnight.

The material was removed from the freezer. Two layers were apparent. Theupper layer was clear and yellow in color. The bottom layer was a orangeand cloudy. The material was poured cold into a separatory funnel. Thetop layer was hexane and the desired product. The bottom layer wasextracted with hexane (6×200 ml), separation occurred easily. Thecombined extracts were dried over anhydrous magnesium sulfate andfiltered, rinsing the solids with hexane. The solvent was stripped to anapproximate volume of 750 ml on a rotary evaporator with the temperaturenot exceeding 24° C. The remaining solvent was stripped off using avacuum/air bubbling set-up at room temperature to give the desiredproduct in 67% yield.

Example 3 Preparation of Butadiene-Acrylonitrile Bismaleimide

Amino-terminated butadiene-acrylonitrile (sold as Hycar resin 1300 X42ATBN by BF Goodrich, in which the m and n depicted in the structure areintegers to provide a number average molecular weight of 3600) (450 g,500 mmol based on amine equivalent weight AEW=450 g) was dissolved inCHCl₃ (1000 mL) in a 3 L four-necked flask equipped with additionfunnel, mechanical stirrer, internal temperature probe and nitrogeninlet/outlet. The stirred solution was placed under nitrogen and cooledon an ice bath. The addition funnel was charged with maleic anhydride(98.1 g, 1 mol) in CHCl₃ (50 mL) and this solution was added to thereaction over 30 minutes, maintaining the internal reaction temperaturebelow 10° C. This mixture was stirred for 30 minutes on ice, thenallowed to warm to room temperature and stirred for an additional 4hours. To the resulting slurry was added acetic anhydride (Ac₂O) (653.4g, 6 mol), triethyl amine (Et₃N) (64.8 g, 0.64 mol) and NaOAc (62.3 g,0.76 mol). The reaction was heated to mild reflux for 5 hours, allowedto cool to room temperature, and subsequently extracted with H₂O(1 L),satd. NaHCO₃ (1 L) and H₂O (2×1 L). Solvent was removed in vacuo toyield the maleimide terminated butadiene acrylonitrile.

Example 4 Preparation of Tris(maleimide) Derived FromTris(epoxypropyl)isocyanurate

Tris(epoxypropyl)isocyanurate (99.0 g, 0.33 mol) is dissolved in THF(500 mL) in a 2 L three-necked flask equipped with mechanical stirrer,internal temperature probe and nitrogen inlet/oulet. To this solution isadded hyroxyphenylmaleimide (189.2 g, 1 mol) and benzyldimethylamine(1.4 g, 0.05 wt. %). The solution is heated to 80° C. for 7 hours. Thereaction is allowed to cool to room temperature, is filtered, and thefiltrant washed with 5% HCl_(aq) (500 mL) and distilled H₂O (1 L). Theresulting solid, triazinetris(maleimide), is vacuum dried at roomtemperature.

Example 5 Preparation of Maleimidoethylpalmitate

Palmitoyl chloride (274.9 g, 1 mol) is dissolved in Et₂O (500 mL) in a 2L three-necked flask equipped with mechanical stirrer, internaltemperature probe, addition funnel and nitrogen inlet/outlet. NaHCO₃(84.0 g, 1 mol) in distilled H₂O (500 mL) is added with vigorousstirring and the solution cooled on an ice bath under nitrogen. Theaddition funnel is charged with hydroxyethylmaleimide (141 g, 1 mol) inEt₂O (100 mL) and this solution added to the reaction over a period of30 minutes, maintaining an internal T<10° C. during the addition. Thereaction is stirred for another 30 minutes on ice, then allowed to warmto room temperature and stirred for 4 hours. The reaction is transferredto a separatory funnel and the isolated organic layer washed withdistilled H₂O (500 mL), 5% HCl_(aq) (500 mL) and distilled H₂O (2×500mL). The organics are isolated, dried over MgSO₄ anhyd., filtered andsolvent removed in vacuo to yield the aliphatic maleimide.

Example 6 Preparation of Bismaleimide Derived from5-Isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane

5-Isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane (111.15 g,0.5 mol) is solvated in THF (500 mL) in a 1 L three-necked flaskequipped with mechanical stirrer, addition funnel and nitrogeninlet/outlet. The reaction is placed under nitrogen, and dibutyltindilaurate (cat. Sn^(II)) (6.31 g, 10 mmol) and hydroxyethylmaleimide(141 g, 1 mol) are added with stirring, and the resulting mixture heatedfor 4 hours at 70° C. The addition funnel is charged withhydroxyethylmaleimide (141 g, 1 mol) dissolved in THF (100 mL). Thissolution is added to the isocyanate solution over 30 minutes, and theresulting mixture heated for an additional 4 hours at 70° C. Thereaction is allowed to cool to room temperature and solvent removed invacuo. The remaining oil is dissolved in CH₂Cl₂ (1 L) and washed with10% HCl_(aq) (1 L) and distilled H₂O (2×1 L). The isolated organics aredried over MgSO₄, filtered and the solvent removed in vacuo to yield themaleimide.

Example 7 Preparation of Dimer Divinyl Ether Derived From Pripol 2033

“Dimer Divinyl Ether” (and Cyclic Isomers)

Bis(1,10-phenanthroline)Pd(OAc)₂ (0.21 g, 0.54 mmol) was dissolved in amixture of butyl vinyl ether (8.18 g, 81.7 mmols), heptane (100 mL) and“dimer diol” (sold as Pripol 2033 by Unichema, 15.4 g, 27.2 mmol) in 2 Lthree-necked flask equipped with a mechanical stirrer under nitrogen.This solution was heated to light reflux for 6 h. The solution wasallowed to cool to room temperature and subsequently poured ontoactivated carbon (20 g) and stirred for 1 hour. The resulting slurry wasfiltered, and excess butyl vinyl ether and heptane were removed in vacuoto yield the divinyl ether as a yellow oil. The product exhibitedacceptable ¹H NMR, FT-IR and ¹³C NMR spectral characteristics. Typicalviscosity ˜100 cPs.

Example 8 Preparation of Dimer Diacrylate Derived from Dimer Diol(Pripol 2033)

A dimer diol (sold as Pripol 2033 by Unichema, 284.4 g, 500 mmol) isdissolved in dry acetone (500 mL) in a 1 L three-necked flask equippedwith mechanical stirrer, addition funnel and internal temperature probeunder nitrogen. Triethylamine (101.2 g, 1 mol) is added to this solutionand the solution cooled to 4° C. on an ice bath. Acryloyl chloride (90.5g, 1 mol) solvated in dry acetone (100 mL) is charged into the additionfunnel and added to the stirred reaction solution over the course of 60minutes, maintaining an internal temperature <10° C. This solution isstirred on ice for an additional 2 hours, then allowed to warm to roomtemperature and stirred for 4 hours. Bulk solvent is removed via arotary evaporator, and the remaining residue solvated in CH₂Cl₂ (1 L).This solution is washed with 5% HCl_(aq) (800 mL), and H₂O (2×800 mL).The isolated organics are dried over MgSO₄ anhyd. and filtered, and thesolvent removed in vacuo to yield the diacrylate as an oil.

Example 9 Preparation of N-ethylphenyl Maleimide

4-Ethyl aniline (12.12 g) was dissolved in 50 ml of anhydrous ethylether and slowly added to a stirred solution of 9.81 g of maleicanhydride in 100 ml of anhydrous ethyl ether chilled in an ice bath.After completion of the addition, the reaction mixture was stirred for30 minutes. The light yellow crystals were filtered and dried. Aceticanhydride (200 ml) was used to dissolve the maleamic acid and 20 g ofsodium acetate. The reaction mixture was heated in an oil bath at 160°C. After 3 hours of reflux, the solution was cooled to room temperature,placed in a 1 L beaker in ice water and stirred vigorously for 1 hour.The product was suction-filtered and recrystallized in hexane. Thecollected crystalline material was dried at 50° C. in a vacuum ovenovernight. FTIR and NMR analysis showed the characteristics of ethylmaleimide.

Example 10 Preparation of Bis(alkenylsulfide)

Dimer acid (sold under the trademark Empol 1024 by Unichema) (574.6 g, 1mol) and propargyl alcohol (112.1 g, 2 mol) are solvated in toluene (1L) in a 3 L three-necked flask equipped with mechanical stirring and aDean-Stark distillation apparatus. Concentrated H₂SO₄ (6 mL) is addedand the solution refluxed for 6 hours until 36 mL of H₂O isazeotropically distilled. The solution is allowed to cool to roomtemperature, is washed with H₂O (2×1 L), dried over MgSO₄ anhyd. and thesolvent removed in vacuo to yield the propargyl ester intermediate as anoil.

This ester intermediate (650.7 g, 1 mol) is solvated in THF (200 mL) ina 1 L three-necked flask equipped with reflux condenser, mechanicalstirrer and internal temperature probe under nitrogen. Lauryl mercaptan(404.8 g, 2 mol) and 2,2′-azobis(2,4-dimethylpentanenitrile) (sold underthe trademark Vazo 52 by DuPont) (11 g) are added and the resultingmixture heated to 70° C. on an oil bath with stirring for 7 hours. Thereaction is allowed to cool to room temperature and solvent removed invacuo to yield the alkenyl sulfide as an oil.

Example 11 Package Encapsulant Compositions

Package encapsulant compositions were prepared by mixing together theorganic components and then by blending the components with a silicafiller in a weight percent ratio of 17% organic to 83% silica under highshear until homogeneous. The silica was FB-6S silica from Denka. Theresulting compositions were light yellow slurries. The organiccomponents, silica ratio by weight, glass transition temperature (Tg),and coefficient of thermal expansion (CTE) are reported here:

Composition Sample 11-A Sample 11-B Sample 11-C Sample 11-D MaleimideN-4-butyl- N-4-ethyl- Dimer Bismaleimide phenyl phenyl diamine *maleimide maleimide bismaleimide  1.0 g 22.9 g 20.1 g  1.0 g 82.0 wt % 51.9 wt %  48.7 wt %  82.0 wt %  Vinyl-t- 20.4 g 20.4 g  0.2 g  0.2 gbutyl- 46.2 wt %  49.4 wt %  16.4 wt %  16.4 wt %  benzoate Dicumyl 0.45g 0.40 g 0.01 g 0.01 g peroxide 1.0 wt % 1.0 wt % 0.8 wt % 0.8 wt %Methacyloxy 0.40 g 0.40 g 0.01 g 0.01 g trimethoxy- 0.9 wt % 1.0 wt %0.8 wt % 0.8 wt % silan Tg 140° C. 145° C. 42° C. 37° C. CTE 16 ppm/° C.15 ppm/° C. 16 ppm/° C. 15 ppm/° C. *(prepared from polytetramethyleneoxide-di-p-aminobenzoate, sold as Versalink P-650 by Henkel)

Example 12 Reworkability

Each composition 11-A to 11-D was tested for reworkability using as atest vehicle a 250×250 mil² silicon die bonded with the composition to aFR-4 circuit board substrate. The encapsulant composition was dispensedonto the chip adhered to the substrate and the assembly cured at 160° C.for 30 minutes. After the assembly again reached room temperature, asponge was saturated with methyl isobutyl ketone and used to wipe theencapsulant in a continuous, circular motion. The encapsulant wasgradually softened, and it dissolved within 10 minutes sufficiently toleave no residue on the substrate.

This Example demonstrates that these compositions can be made to bereworkable.

Example 13 UV and Thermally Curable Compositions

Composition 13-A

A package encapsulant composition was prepared by combining thefollowing ingredients with vigorous manual mixing until a homogenouspaste was obtained:

Bismaleimide

(prepared from polytetramethylene oxide-di-p-aminobenzoate,

sold as Versalink P-650 by Henkel) 1.01 g

Cyclohexanedimethanol divinylether

(International Specialty Products): 0.19 g

α,α-Dimethoxy-α-phenylacetophenone

(sold as Irgacure 651 by Ciba Specialty Chemicals) 0.06 g

Hydrophilic Fused Silica

(sold by Denka, ˜5 micron) 3.78 g

A 250 mil×250 mil silicon die placed on FR-4 laminate was encapsulatedwith the above paste and irradiated for 30 seconds using a pulsed xenonUV source (RC-500B Pulsed UV Curing System, Xenon Corporation). Theencapsulant exhibited a hard, fully cured surface and held the diefirmly to the laminate material when force was applied. The sampleassembly was subsequently placed in a 175° C. oven for 20 minutes. Theencapsulated die was allowed to cool to room temperature and thenforcibly removed from the laminate. No regions of uncured encapsulantwere detected around the die edge, the laminate/adhesive interface orthe adhesive/air surface interface.

Composition 13-B

A package encapsulant composition was prepared by combining thefollowing ingredients with vigorous manual mixing until a homogenouspaste was obtained:

Bismaleimide

(prepared from polytetramethylene oxide-di-p-aminobenzoate,

sold as Versalink P-650 by Henkel) 1.01 g

Cyclohexanedimethanol divinylether

(International Specialty Products): 0.19 g

t-Butyl-2-ethylhexanoate 0.03 g

Hydrophilic Fused Silica

(sold by Denka, ˜5 micron) 3.78 g

A 250 mil×250 mil silicon die placed on FR-4 laminate was encapsulatedwith the above paste and placed in a 150° C. oven for 30 min. The testassembly was allowed to cool to room temperature and the die wasforcibly removed from the laminate. No regions of uncured encapsulantwere detected around the die edge, the laminate/adhesive interface orthe adhesive/air surface interface.

Example A Preparation of 6-maleimidocaproic acid

6-maleimidocaproic acid

The acid functional maleimide, 6-maleimidocaproic acid, was synthesizedusing known methodology.¹ Aminocaproic acid (100 g, 7.6×10⁻¹ mols) wasdissolved in glacial acetic acid (50 mL) in a 500 mL four-necked flaskequipped with mechanical stirring, an internal temperature probe and anaddition funnel. The addition funnel was charged with a solution ofmaleic anhydride (74.8 g, 7.6×10⁻¹ mols) dissolved in acetonitrile (75mL). This solution was added to the aminocaproic acid at roomtemperature dropwise over 1 hour, maintaining an internal reactiontemperature less than 35° C. The reaction was stirred for three hoursafter the addition was complete. The reaction slurry was filtered, andthe isolated filtrate was dried in a vacuum oven (P-25 T) overnight at70° C. to yield 166 g of off white solid (95%). The product amic acidexhibited FT-IR and ¹H NMR spectral characteristics consistent withliterature data.

The amic acid described above (166 g, 7.2×10⁻¹ mols) was solvated in asolution of toluene (200 mL), benzene (200 mL) and triethylamine (211mL, 1.51 mol) in a 1 L three-necked flask equipped with mechanicalstirring and a Dean-Stark trap under nitrogen. This solution was heatedto reflux for 4 h and the water produced collected in the Dean-Starktrap. Distilled water (400 mL) was added to the reaction flask todissolve the triethylammonium salt of the product which largelyseparated from the bulk solution during the reaction. This aqueous layerwas isolated, acidified to pH˜1 with 50% HCl, and extracted with ethylacetate (600 mL). This organic layer was washed with distilled water(400 mL). The isolated organic layer was dried over MgSO₄, followed bysolvent removal in vacuo to yield an off white solid (76.2 g, 50%). Theproduct 6-maleimidocaproic acid was spectrographically identical toliterature material by FT-IR and ¹H NMR.

Example B Preparation of “Dimer Diester Bismaleimide”

“Dimer Diester Bismaleimide” (and Cyclic Isomers)

Pripol 2033 (“dimer diol”, Uniqema, 92.4 g, 1.69×10⁻¹ mols),6-maleimidocaproic acid (75.0 g, 3.55×10⁻¹ mols) and H₂SO₄ (0.50 mL,˜8.5×10⁻³ mols) were slurried in toluene (300 mL) in a 1 L four-neckedflask equipped with mechanical stirrer, a Dean-Stark trap and aninternal temperature probe under nitrogen. The reaction was heated tolight reflux for two hours and the water evolved collected in theDean-Stark trap. The trap was drained and ˜50 mL of toluene solvent wasdistilled off of the reaction to remove trace moisture and drive theesterification equilibrium to completion. The reaction was allowed tocool to room temperature, additional toluene (100 mL) was added (on thelaboratory scale it is preferable to add diethyl ether in place oftoluene at this point), and the solution was washed with saturatedNaHCO₃ aq. (300 mL) and distilled water (300 mL). The organic layer wasisolated and dried over anhydrous MgSO₄, and the solvent removed invacuo to yield an orange oil (107.2 g, 68%). The material can be furtherpurified by eluting a toluene solution of the resin through a short plugof silica or alumina. This liquid bismaleimide resin exhibitedacceptable FT-IR, ¹H NMR, and ¹³C NMR data. Typical η˜2500 cPs.

Example C Preparation of “Decane Diol Diester Bismaleimde”

Decane Diol Diester Bismaleimide

The general procedure described in Example B. was applied substitutingdecane diol (29.5 g, 1.69×10⁻¹ mols) for Pripol 2033. This processyielded a solid, moderately soluble bismaleimide (54.9 g, 58%). Theproduct exhibited satisfactory FT-IR and ¹H NMR data.

Example D Preparation of “Glycerol Triester Tris(maleimide)”

The protocol outlined in example B. was utilized substituting glycerol(10.4 g, 1.13×10⁻¹ mol) for Pripol 2033. The product was a viscousliquid which exhibited acceptable FT-IR and ¹H NMR data.

Example E Preparation of “Bis(m-nitrobenzyl carbamate) of IPDI”

Bis(m-nitrobenzyl carbamate) of IPDI

Isophorone diisocyanate (“IPDI”, 100.0 g, 4.5×10⁻¹ mols), m-nitrobenzylalcohol (137.8 g, 9.0×10⁻¹ mols) and dibutyl tin dilaurate (2.8 g,4.5×10⁻³ mols) were solvated in dry toluene (1500 mL) in a 2Lthree-necked flask equipped with mechanical stirrer, reflux condenserand internal temperature probe under nitrogen. The resulting solutionwas heated to 90° C. for 4 h. No isocyanate band was observed in the IRof the solids portion of the sample. The solution was allowed to cool toroom temperature and washed with distilled H₂O (100 mL). The organiclayer was isolated and solvent removed in vacuo to yield a yellow liquidwhich exhibited acceptable FT-IR and ¹H NMR characteristics.

Example F Preparation of “Bis(m-aminobenzyl carbamate) of IPDI”

Bis(m-aminobenzyl carbamate) of IPDI

The dinitro compound from Example E. (8.28 g, 1.57×10⁻² mols) wasdissolved in ethanol (100 mL) in a 500 mL three-necked round bottomflask equipped with magnetic stirring under nitrogen. Cyclohexene (28.6mL, 2.82×10⁻¹ mols) was added, followed by 5% Pd/C (4.14 g). Theresulting slurry was refluxed lightly for 6.5 h. The FT-IR of a filteredaliquot of this solution exhibited no nitro stretching bands at 1529cm⁻¹ and 1352 cm⁻¹. The bulk solution was allowed to cool to roomtemperature and filtered. Solvent was removed in vacuo to yield a yellowsemisolid (6.6 g, 90%) which exhibited acceptable FT-IR and ¹H NMRspectral characteristics.

Example G Preparation of “Bis(m-maleimidobenzyl carbamate) of IPDI”

Bis(m-maleimidobenzyl carbamate) of IPDI

The diamine from Example F (6.6 g, 1.41×1⁻² mols) was solvated inacetone (60 mL) in a 250 mL four-necked flask equipped with magneticstirrer and addition funnel under nitrogen and cooled to 4° C. Maleicanhydride (2.76 g, 2.82×10⁻² mols) dissloved in acetone (20 mL) wasadded over the course of 30 minutes. The resulting solution was stirredat 4° C. for for 1 h, and subsequently was allowed to warm to roomtemperature and stirred overnight. FT-IR analysis indicated no maleicanhydride remained as judged by the absence of the anhydride stretchingband at ˜1810 cm⁻¹.

To the above amic acid solution was added acetic anhydride (8.5 mL,9.0×10⁻² mols), triethylamine (1.26 mL, 9.0×10⁻³ mols) and sodiumacetate (0.88 g, 1.1×10⁻² mols). The resulting solution was refluxedlightly for 4 h under nitrogen. The reaction was allowed to cool to roomtemperature and bulk solvent was removed in vacuo. The resulting viscousliquid was resolvated in methylene chloride (200 mL) and extracted withdistilled water (3×200 mL). The organics were then dried over MgSO₄anhyd., filtered and solvent removed in vacuo to yield a light brownsolid (6.75 g, 76%). This material exhibited acceptable FT-IR and ¹H NMRspectral features.

Example H Preparation of “Bis(m-nitrobenzyl carbamate) of DDI 1410”

“Bis(m-nitrobenzyl carbamate) of DDI 1410” (and cyclic isomers)

DDI 1410 (Henkel, “Dimer Diisocyanate”, 99.77 g, 1.65×10⁻¹ mols based on13.96% NCO), m-nitrobenzyl alcohol (50.8 g, 3.32×10⁻¹ mols) anddibutyltin dilaurate (0.5 mL, 8.3×10⁻⁴ mols) were solvated in toluene(150 mL) in a 1 L four-necked flask equipped with mechanical stirrer,reflux condensor and internal temperature probe under nitrogen. Thereaction was heated to 85° C. for 2.5 h. FT-IR analysis of an aliquot ofthe reaction indicated complete comsumption of isocyanate functionalityas judged by the lack of a band at 2272 cm⁻¹. Solvent was removed fromthe reaction in vacuo to yield a yellow oil which solidified uponstanding at room temperature (152.4 g, 102% (trace toluene)). This solidexhibited satisfactory FT-IR and ¹H NMR spectral features.

Example I Preparation of “Bis(m-aminobenzyl carbamate) of DDI 1410”

“Bis(m-aminobenzyl carbamate) of DDI 1410” (and cyclic isomers)

The diamine product of Example H (39.6 g, 4.32×10⁻² mols) and stannouschloride dihydrate (97.55 g, 4.32×10⁻¹ mols) were slurried in ethylacetate (300 mL) in a 1 L three-necked flask equipped with mechanicalstirrer and a reflux condenser under nitrogen. The reaction was heatedto light reflux and stirred vigorously for 3 h. The solution was allowedto cool to room temperature and brought to pH 7-8 with a solution ofsaturated sodium bicarbonate. The mixture was pushed through a 25 micronfilter to yield a mixture which separated into a cloudy aqueous layerand a moderately clear organic layer. The aqueous layer was isolated andwashed with ethyl acetate (100 mL). The organic layers were combined,washed with distilled water (300 mL) and dried over anhydrous MgSO₄. Theslurry was filtered and solvent removed from the filtrate in vacuo toyield yellow, sticky solid (33.8 g, 92%).

Example J Preparation of “Bis(m-maleimidobenzyl carbamate) of DDI 1410”

“Bis(m-maleimidobenzyl carbamate) of DDI 1410” (and cyclic isomers)

Maleic anhydride (15.4 g, 1.57×10⁻² mols) was dissolved in acetone g(300 mL) in a 2 L four-necked flask equipped with mechanical stirrer,internal temperature probe and addition funnel under nitrogen. Thissolution was cooled to ˜4° C. on an ice bath. A solution of the diamineprepared in Example I (63.4 g, 7.48×10⁻² mols) in acetone (70 mL) wascharged to the addition funnel and added to the maleic anhydridesolution over a period of 30 minutes maintaining an internal temperatureof <10° C. The resulting solution was stirred for 1 h and subsequentlyallowed to warm to room temperature and stir for 2 h.

To this solution of amic acid was added acetic anhydride (24.7 mL,2.62×10⁻¹ mols), triethylamine (6.25 mL, 4.48×10⁻² mols) and manganeseacetate tetrahydrate (0.37 g, 1.50×10⁻³ mols). This solution was heatedto light reflux for 6.5 h, then allowed to cool to room temperature.Bulk solvent was removed in vacuo, and the resulting dark liquid wasdissolved in diethyl ether (500 mL). This solution was washed with dist.H₂O (500 mL). The isolated organic layer was then washed with saturatedNaHCO₃ aq. (500 mL) and again with dist. H₂O (500 mL). The organics wereisolated, dried over anhyd. MgSO₄, and solvent removed in vacuo to yielda viscous orange oil. This material exhibited FT-IR, ¹H NMR and ¹³C NMRspectral features consistent with the expected bismaleimide product.

What is claimed is:
 1. A curable package encapsulant compositioncomprising a maleimide compound, and a curing initiator selected fromthe group consisting of a free-radical initiator, a photoinitiator, anda combination of those, the maleimide compound having the formula:

in which n is 1 to 6 and (a) R¹ is H or an alkyl group having 1 to 5carbon atoms; (b) Ar is an aromatic group selected from the aromaticgroups having the structures:

(c) Q is a linear or branched chain alkyl, alkyloxy, alkyl amine, alkylsulfide, alkylene, alkyleneoxy, alkylene amine, alkylene sulfide, aryl,aryloxy, or aryl sulfide species having up to about 100 atoms in thechain, which may contain saturated or unsaturated cyclic or heterocyclicsubstituents pendant from the chain or as part of the chain, and inwhich any heteroatom present may or may not be directly attached to Ar;or Q is a urethane having the structure:

 in which each R² independently is an alkyl, aryl, or arylalkyl grouphaving 1 to 18 carbon atoms; R³ is an alkyl or alkyloxy chain having upto 100 atoms in the chain, which chain may contain aryl substituents; Xis O, S, N, or P; and v is 0 to 50; or Q is an ester having thestructure:

 in which R³ is an alkyl or alkyloxy chain having up to 100 atoms in thechain, which chain may contain aryl substituents; or Q is a siloxanehaving the structure: —(CR¹ ₂)_(e)—(SiR⁴ ₂—O)_(f)—SiR⁴ ₂—(CR¹ ₂)_(g)— inwhich the R¹ substituent independently for each position is H or analkyl group having 1 to 5 carbon atoms, and the R⁴ substituentindependently for each position is an alkyl group having 1 to 5 carbonatoms or an aryl group, and e and g are independently 1 to 10 and f is 1to
 50. 2. The curable package encapsulant composition according to claim1 in which Q is the urethane.
 3. A curable package encapsulantcomposition comprising a maleimide compound, and a curing initiatorselected from the group consisting of a free-radical initiator, aphotoinitiator, and a combination of those, the maleimide compoundhaving the formula:

in which n is 1 to 6 and (a) R¹ is H or an alkyl group having 1 to 5carbon atoms; (b) Ar is an aromatic group selected from the aromaticgroups having the structures:

(c) Q is a linear or branched chain alkyl amine, alkyl sulfide, alkyleneamine, alkylene sulfide, aryl, aryloxy, or aryl sulfide species havingup to about 100 atoms in the chain, which may contain saturated orunsaturated cyclic or heterocyclic substituents pendant from the chainor as part of the chain, and in which any heteroatom present may or maynot be directly attached to Ar; or Q is a urethane having the structure:

 in which each R² independently is an alkyl, aryl, or arylalkyl grouphaving 1 to 18 carbon atoms; R³ is an alkyl or alkyloxy chain having upto 100 atoms in the chain, which chain may contain aryl substituents; Xis O, S, N, or P; and v is 0 to 50; or Q is an ester having thestructure:

 in which R³ is an alkyl or alkyloxy chain having up to 100 atoms in thechain, which chain may contain aryl substituents.
 4. The curable packageencapsulant composition according to claim 3 in which Q is the urethane.5. The curable package encapsulant composition according to claim 3 inwhich Q is the ester.
 6. A curable package encapsulant compositioncomprising a maleimide compound and a curing initiator selected from thegroup consisting of a free-radical initiator, a photoinitiator, and acombination of those, the maleimide compound having the formula

in which n is 1 to 6, and (a) R¹ is H or an alkyl having 1 to 5 carbonatoms; (b) Z is a linear or branched chain alkyl amine, alkyl sulfide,alkylene amine, alkylene sulfide, aryl, aryloxy, or aryl sulfide specieshaving up to about 100 atoms in the chain, which may contain saturatedor unsaturated cyclic or heterocyclic substituents pendant from thechain or as part of the chain, and in which any heteroatom present mayor may not be directly attached to Ar; or Z is a urethane having thestructure:

 in which each R² independently is an alkyl, aryl, or arylalkyl grouphaving 1 to 18 carbon atoms; R³ is an alkyl or alkyloxy chain having upto 100 atoms in the chain, which chain may contain aryl substituents; Xis O, S, N, or P; and v is 0 to 50; or Z is a siloxane having thestructure: —(CR¹ ₂)_(e)—[SiR⁴ ₂—O]_(f)—SiR⁴ ₂—(CR¹ ₂)_(g)— in which theR¹ substituent independently for each position is H or an alkyl grouphaving 1 to 5 carbon atoms, and the R⁴ substituent independently foreach position is an alkyl group having 1 to 5 carbon atoms or an arylgroup, and e and g are independently 1 to 10, and f is 1 to 50; or Z isan ester having the structure:

 in which R³ is an alkyl or alkyloxy chain having up to 100 atoms in thechain, which chain may contain aryl substituents; (c) Ar is an aromaticgroup selected from group of aromatic groups having the structures:

 in which p is 1 to 100; R⁵, R⁶, and R⁷ are a linear or branched chainalkyl, alkyloxy, alkyl amine, alkyl sulfide, alkylene, alkyleneoxy,alkylene amine, alkylene sulfide, aryl, aryloxy, or aryl sulfide specieshaving up to about 100 atoms in the chain, which may contain saturatedor unsaturated cyclic or heterocyclic substituents pendant from thechain or as part of the backbone in the chain, and in which anyheteroatom present may or may not be directly attached to the aromaticring; or R⁵, R⁶, and R⁷ are a siloxane having the structure —(CR¹₂)_(e)—[SiR⁴ ₂—O]_(f)—R⁴ ₂—(CH₃)_(g) — in which the R¹ substituent is Hor an alkyl group having 1 to 5 carbon atoms and the R⁴ substituentindependently for each position is an alkyl group having 1 to 5 carbonatoms or an aryl group, and e is 1 to 10 and f is 0 to
 50. 7. Thecurable package encapsulant composition according to claim 6 in which Zis the urethane.
 8. The curable package encapsulant compositionaccording to claim 6 in which Z is the siloxane.
 9. The curable packageencapsulant composition according to claim 6 in which Z is the ester.10. A curable package encapsulant composition comprising a maleimidecompound and a curing initiator selected from the group consisting of afree-radical initiator, a photoinitiator, and a combination of those,the maleimide compound having the formula

which n is 1 to 6, and (a) R¹ is H or an alkyl having 1 to 5 carbonatoms; (b) Ar is an aromatic group selected from group of aromaticgroups having the structures:

 in which p is 1 to 100; R⁵, R⁶, and R⁷ are a linear or branched chainalkyl, alkyloxy, alkyl amine, alkyl sulfide, alkylene, alkyleneoxy,alkylene amine, alkylene sulfide, aryl, aryloxy, or aryl sulfide specieshaving up to about 100 atoms in the chain, which may contain saturatedor unsaturated cyclic or heterocyclic substituents pendant from thechain or as part of the backbone in the chain, and in which anyheteroatom present may or may not be directly attached to the aromaticring; or R⁵, R⁶, and R⁷ are a siloxane having the structure —(CR¹₂)_(e)—[SiR⁴ ₂—O]_(f)—R⁴ ₂—(CH₃)_(g)— in which the R¹ substituent is Hor an alkyl group having 1 to 5 carbon atoms and the R⁴ substituentindependently for each position is an alkyl group having 1 to 5 carbonatoms or an aryl group, and e is 1 to 10 and f is 0 to
 50. 11. A curablepackage encapsulant composition comprising a vinyl compound, and acuring initiator selected from the group consisting of a free-radicalinitiator, a photoinitiator, and a combination of those, the vinylcompound having the formula

in which n is 1 to 6, and (a) R¹ and R² are H or an alkyl group having 1to 5 carbon atoms, or together form a 5 to 9 membered ring with thecarbons forming the vinyl group; (b) B is C, S, N, O, C(O), O—C(O),C(O)—O, C(O)NH or C(O)N(R⁸), in which R⁸ is an alkyl group having 1 to 5carbon atoms; (c) each Ar is an aromatic group selected from the groupof aromatic groups having the structures:

(d) Q is a linear or branched chain alkyl amine, alkyl sulfide, alkyleneamine, alkylene sulfide, aryl, aryloxy, or aryl sulfide species havingup to about 100 atoms in the chain, which may contain saturated orunsaturated cyclic or heterocyclic substituents pendant from the chainor as part of the chain, and in which any heteroatom present may or maynot be directly attached to Ar; or Q is a urethane having the structure:

 in which each R² independently is an alkyl, aryl, or arylalkyl grouphaving 1 to 18 carbon atoms; R³ is an alkyl or alkyloxy chain having upto 100 atoms in the chain, which chain may contain aryl substituents; Xis O, S, N, or P; and v is 0 to 50; or Q is an ester having thestructure:

 in which R³ is an alkyl or alkyloxy chain having up to 100 atoms in thechain, which chain may contain aryl substituents; or Q is a siloxanehaving the structure: —(CR¹ ₂)_(e)—(SiR⁴ ₂—O)_(f)—SiR⁴ ₂—(CR¹ ₂)_(g)— inwhich the R¹ substituent independently for each position is H or analkyl group having 1 to 5 carbon atoms, and the R⁴ substituentindependently for each position is an alkyl group having 1 to 5 carbonatoms or an aryl group, and e and g are independently 1 to 10 and f is 1to
 50. 12. The curable package encapsulant composition according toclaim 11 in which Q is the urethane.
 13. The curable package encapsulantcomposition according to claim 11 in which Q is the ester.
 14. Thecurable package encapsulant composition according to claim 11 in which Qis the siloxane.
 15. A curable package encapsulant compositioncomprising a vinyl compound, and a curing initiator selected from thegroup consisting of a free-radical initiator, a photoinitiator, and acombination of those, the vinyl compound having the formula

in which n is 1 to 6, and (a) R¹ and R² are H or an alkyl group having 1to 5 carbon atoms, or together form a 5 to 9 membered ring with thecarbons forming the vinyl group; (b) B is C, S, N, C(O)NH or C(O)N(R⁸),in which R⁸ is an alkyl group having 1 to 5 carbon atoms; (c) Ar is anaromatic group selected from the aromatic groups having the structures:

(d) Q is a linear or branched chain alkyl, alkyloxy, alkyl amine, alkylsulfide, alkylene, alkyleneoxy, alkylene amine, alkylene sulfide, aryl,aryloxy, or aryl sulfide species having up to about 100 atoms in thechain, which may contain saturated or unsaturated cyclic or heterocyclicsubstituents pendant from the chain or as part of the chain, and inwhich any heteroatom present may or may not be directly attached to Ar;or Q is a urethane having the structure:

 in which each R² independently is an alkyl, aryl, or arylalkyl grouphaving 1 to 18 carbon atoms; R³ is an alkyl or alkyloxy chain having upto 100 atoms in the chain, which chain may contain aryl substituents; Xis O, S, N, or P; and v is 0 to 50; or Q is an ester having thestructure:

 in which R³ is an alkyl or alkyloxy chain having up to 100 atoms in thechain, which chain may contain aryl substituents; or Q is a siloxanehaving the structure: —(CR¹ ₂)_(e)—(SiR⁴ ₂—O)_(f)—SiR⁴ ₂—(CR¹ ₂)_(g)— inwhich the R¹ substituent independently for each position is H or analkyl group having 1 to 5 carbon atoms, and the R⁴ substituentindependently for each position is an alkyl group having 1 to 5 carbonatoms or an aryl group, and e and g are independently 1 to 10 and f is 1to
 50. 16. The curable package encapsulant composition according toclaim 15 in which Q is the urethane.
 17. The curable package encapsulantcomposition according to claim 15 in which Q is the ester.
 18. Thecurable package encapsulant composition according to claim 15 in which Qis the siloxane.
 19. A curable package encapsulant compositioncomprising a vinyl compound, and a curing initiator selected from thegroup consisting of a free-radical initiator, a photoinitiator, and acombination of those, the vinyl compound having the formula

in which n is 1 to 6, and (a) R¹ and R² are H or an alkyl group having 1to 5 carbon atoms, or together form a 5 to 9 membered ring with thecarbons forming the vinyl group; (b) B is C, S, N, O, C(O), O—C(O),C(O)—O, C(O)NH or C(O)N(R⁸), in which R⁸ is an alkyl group having 1 to 5carbon atoms; (c) Ar is an aromatic group selected from the aromaticgroups having the structures:

(d) Q is a linear or branched chain alkyl, alkyloxy, alkyl amine, alkylsulfide, alkylene, alkylene oxide, alkylene amine, alkylene sulfide,aryl, aryloxy, or aryl sulfide species having up to about 100 atoms inthe chain, which may contain saturated or unsaturated cyclic orheterocyclic substituents pendant from the chain or as part of thechain, and in which any heteroatom present may or may not be directlyattached to Ar; or Q is a urethane having the structure:

 in which each R² independently is an alkyl, aryl, or arylalkyl grouphaving 1 to 18 carbon atoms; R³ is an alkyl or alkyloxy chain having upto 100 atoms in the chain, which chain may contain aryl substituents; Xis O, S, N, or P; and v is 0 to 50; or Q is an ester having thestructure:

 in which R³ is an alkyl or alkyloxy chain having up to 100 atoms in thechain, which chain may contain aryl substituents; or Q is a siloxanehaving the structure: —(CR¹ ₂)_(e)—(SiR⁴ ₂—O)_(f)—SiR⁴ ₂—(CR¹ ₂)_(g)— inwhich the R¹ substituent independently for each position is H or analkyl group having 1 to 5 carbon atoms, and the R⁴ substituentindependently for each position is an alkyl group having 1 to 5 carbonatoms or an aryl group, and e and g are independently 1 to 10 and f is 1to
 50. 20. The curable package encapsulant composition according toclaim 19 in which Q is the urethane.
 21. The curable package encapsulantcomposition according to claim 19 in which Q is the ester.
 22. Thecurable package encapsulant composition according to claim 19 in which Qis the siloxane.
 23. A curable package encapsulant compositioncomprising a vinyl compound, and a curing initiator selected from thegroup consisting of a free-radical initiator, a photoinitiator, and acombination of those, the vinyl compound having the formula

in which n is 1 to 6, and (a) R¹ and R² are H or an alkyl group having 1to 5 carbon atoms, or together form a 5 to 9 membered ring with thecarbons forming the vinyl group; (b) B is C, S, N, O, C(O), O—C(O),C(O)—O, C(O)NH or C(O)N(R⁸), in which R⁸ is an alkyl group having 1 to 5carbon atoms; (c) Q is a urethane having the structure:

 in which each R² independently is an alkyl, aryl, or arylalkyl grouphaving 1 to 18 carbon atoms; R³ is an alkyl or alkyloxy chain having upto 100 atoms in the chain, which chain may contain aryl substituents; Xis O, S, N. or P; and v is 0 to
 50. 24. A curable package encapsulantcomposition comprising a vinyl compound, and a curing initiator selectedfrom the group consisting of a free-radical initiator, a photoinitiator,and a combination of those, the vinyl compound having the formula

in which n is 1 to 6, and (a) R¹ and R² are H or an alkyl group having 1to 5 carbon atoms, or together form a 5 to 9 membered ring with thecarbons forming the vinyl group; (b) B is C, S, N, C(O)NH or C(O)N(R⁸),in which R⁸ is an alkyl group having 1 to 5 carbon atoms; (c) Q is alinear or branched chain alkyl, alkyloxy, alkyl amine, alkyl sulfide,alkylene, alkyleneoxy, alkylene amine, alkylene sulfide, aryl, aryloxy,or aryl sulfide species having up to about 100 atoms in the chain, whichmay contain saturated or unsaturated cyclic or heterocyclic substituentspendant from the chain or as part of the chain, and in which anyheteroatom present may or may not be directly attached to Ar; or Q is aurethane having the structure:

 in which each R² independently is an alkyl, aryl, or arylalkyl grouphaving 1 to 18 carbon atoms; R³ is an alkyl or alkyloxy chain having upto 100 atoms in the chain, which chain may contain aryl substituents; Xis O, S, N, or P; and v is 0 to 50; or Q is an ester having thestructure:

 in which R³ is an alkyl or alkyloxy chain having up to 100 atoms in thechain, which chain may contain aryl substituents; or Q is a siloxanehaving the structure: —(CR¹ ₂)_(e)—(SiR⁴ ₂—O)_(f)—SiR⁴ ₂—(CR¹ ₂)_(g)— inwhich the R¹ substituent independently for each position is H or analkyl group having 1 to 5 carbon atoms, and the R⁴ substituentindependently for each position is an alkyl group having 1 to 5 carbonatoms or an aryl group, and e and g are independently 1 to 10 and f is 1to
 50. 25. The curable package encapsulant composition according toclaim 24 in which Q is the urethane.
 26. The curable package encapsulantcomposition according to claim 24 in which Q is the ester.
 27. Thecurable package encapsulant composition according to claim 24 in which Qis the siloxane.